Photoelectron spectroscopy, adsorption

The pros and cons of oxidative dehydrogenation for alkene synthesis using doped cerianites as solid oxygen carriers are studied. The hydrogen oxidation properties of a set of ten doped cerianite catalysts (Ce0.9X0.1Oy, where X = Bi, In, La, Mo, Pb, Sn, V, W, Y, and Zr) are examined under cyclic redox conditions. X-ray diffraction, X-ray photoelectron spectroscopy, adsorption measurements, and temperature programmed reduction are used to try and clarify structure-activity relationships and the different dopant effects. 

Baillie CA, Watts JF, Castle JE, Determination of the acidity of carbon fiber surfaces by means of X-ray photoelectron spectroscopy adsorption isotherms, J Mater Chem, 2(9), 939-944, 1992. 

Ultraviolet photoelectron spectroscopy (UPS) results have provided detailed infomiation about CO adsorption on many surfaces. Figure A3.10.24 shows UPS results for CO adsorption on Pd(l 10) [58] that are representative of molecular CO adsorption on platinum surfaces. The difference result in (c) between the clean surface and the CO-covered surface shows a strong negative feature just below the Femii level ( p), and two positive features at 8 and 11 eV below E. The negative feature is due to suppression of emission from the metal d states as a result of an anti-resonance phenomenon. The positive features can be attributed to the 4a molecular orbital of CO and the overlap of tire 5a and 1 k molecular orbitals. The observation of features due to CO molecular orbitals clearly indicates that CO molecularly adsorbs. The overlap of the 5a and 1 ti levels is caused by a stabilization of the 5 a molecular orbital as a consequence of fomiing the surface-CO chemisorption bond. 

High quahty SAMs of alkyltrichlorosilane derivatives are not simple to produce, mainly because of the need to carefully control the amount of water in solution (126,143,144). Whereas incomplete monolayers are formed in the absence of water (127,128), excess water results in facile polymerization in solution and polysiloxane deposition of the surface (133). Extraction of surface moisture, followed by OTS hydrolysis and subsequent surface adsorption, may be the mechanism of SAM formation (145). A moisture quantity of 0.15 mg/100 mL solvent has been suggested as the optimum condition for the formation of closely packed monolayers. X-ray photoelectron spectroscopy (xps) studies confirm the complete surface reaction of the —SiCl groups, upon the formation of a complete SAM (146). Infrared spectroscopy has been used to provide direct evidence for the hiU hydrolysis of methylchlorosilanes to methylsdanoles at the soHd/gas interface, by surface water on a hydrated siUca (147). 

At present, most workers hold a more realistic view of the promises and difficulties of work in electrocatalysis. Starting in the 1980s, new lines of research into the state of catalyst surfaces and into the adsorption of reactants and foreign species on these surfaces have been developed. Techniques have been developed that can be used for studies at the atomic and molecular level. These techniques include the tunneling microscope, versions of Fourier transform infrared spectroscopy and of photoelectron spectroscopy, differential electrochemical mass spectroscopy, and others. The broad application of these techniques has considerably improved our understanding of the mechanism of catalytic effects in electrochemical reactions. 

In this chapter, we have chosen from the scientific literature accounts of symposia published at intervals during the period 1920 1990. They are personal choices illustrating what we believe reflect significant developments in experimental techniques and concepts during this time. Initially there was a dependence on gas-phase pressure measurements and the construction of adsorption isotherms, followed by the development of mass spectrometry for gas analysis, surface spectroscopies with infrared spectroscopy dominant, but soon to be followed by Auger and photoelectron spectroscopy, field emission, field ionisation and diffraction methods. 

Gomez-Sainero et al. (11) reported X-ray photoelectron spectroscopy results on their Pd/C catalysts prepared by an incipient wetness method. XPS showed that Pd° (metallic) and Pdn+ (electron-deficient) species are present on the catalyst surface and the properties depend on the reduction temperature and nature of the palladium precursor. With this understanding of the dual sites nature of Pd, it is believed that organic species S and A are chemisorbed on to Pdn+ (SI) and H2 is chemisorbed dissociatively on to Pd°(S2) in a noncompetitive manner. In the catalytic cycle, quasi-equilibrium ( ) was assumed for adsorption of reactants, SM and hydrogen in liquid phase and the product A (12). Applying Horiuti s concept of rate determining step (13,14), the surface reaction between the adsorbed SM on site SI and adsorbed hydrogen on S2 is the key step in the rate equation. 

Electrochemical impedance spectroscopy was used to determine the effect of isomers of 2,5-bis( -pyridyl)-l,3,4-thiadiazole 36 (n 2 or 3) on the corrosion of mild steel in perchloric acid solution <2002MI197>. The inhibition efficiency was structure dependent and the 3-pyridyl gave better inhibition than the 2-pyridyl. X-ray photoelectron spectroscopy helped establish the 3-pyridyl thiadiazoles mode of action toward corrosion. Adsorption of the 3-pyridyl on the mild steel surface in 1M HCIO4 follows the Langmuir adsorption isotherm model and the surface analysis showed corrosion inhibition by the 3-pyridyl derivative is due to the formation of chemisorbed film on the steel surface. 

The most conventional investigations on the adsorption of both modifier and substrate looked for the effect of pH on the amount of adsorbed tartrate and MAA [200], The combined use of different techniques such as IR, UV, x-ray photoelectron spectroscopy (XPS), electron microscopy (EM), and electron diffraction allowed an in-depth study of adsorbed tartrate in the case of Ni catalysts [101], Using these techniques, the general consensus was that under optimized conditions a corrosive modification of the nickel surface occurs and that the tartrate molecule is chemically bonded to Ni via the two carbonyl groups. There were two suggestions as to the exact nature of the modified catalyst Sachtler [195] proposed adsorbed nickel tartrate as chiral active site, whereas Japanese [101] and Russian [201] groups preferred a direct adsorption of the tartrate on modified sites of the Ni surface. 

Recent studies using high resolution electron energy loss and photoelectron spectroscopy to investigate the effect of sulfur on the CO/Ni(100) system are consistent with an extended effect by the impurity on the adsorption and bonding of CO. Sulfur levels of a few percent of the surface nickel atom concentration were found sufficient to significantly alter the surface electronic structure as well as the CO bond strength. 

Buckley, A. N., 1994. A survey of the application of X-ray photoelectron spectroscopy to flotation research. Colloids Surf, 93 159 - 172 Buckley, A. N. and Woods, R., 1995. Identifying chemisorption in the interaction of thiol collectors with sulphide minerals by XPS adsorption of xanthate on silver and silver sulphide. Colloids and Surfaces A Physicochemical and Engineering Aspects, 104,2 - 3 Buckley, A. N. and Woods, R., 1996. Relaxation of the lead-deficient sulphide surface layer on oxidized galena. Journal of Applied Electrochemistry, 26(9) 899 - 907 Buckley, A. N. and Woods, R., 1997. Chemisorption—the thermodynamically favored process in the interaction of thiol collectors with sulphide minerals. Inert. J. Miner. Process, 51 15-26... 

Costa, M. C., Botelho, do Rego A. M., Abrants, L. M., 2002. Characterization of a natural and an electro-oxidized arsenopyrite a study on electro-chemical and X-ray photoelectron spectroscopy. Inter. J. Miner. Process, 65 83 - 108 Dai Jingping, Sun Wei, Cao Limei, Hu Yuehua, 2000. Influence of mechanical excitation on adsorption of sodium diethyl dithioformate on galena and sphalerite. Trans. Nonferrous Met. Soc., China, 10 101 - 105... 

O Dell, C. S., Walker, G. W., Richardson, P. E., 1986. Electrochemistry of the chalcocite-xandiate system. J. Appl. Electrochem., 16 544-554 Opahle, I., Koepemik, K., Eschrig, H., 2000. Full potential band stracture calculation of iron pyrite. Computational Materials Science, 17(2 - 4) 206 - 210 Page, P. W. and Hazell, L. B., 1989. X-ray photoelectron spectroscopy (XPS) studies of potassium amyl xanthate (KAX) adsorption on precipitated PbS related to galena flotation. Inter. J. Miner. Process, 25 87 - 100... 

The significance of the development of photoelectron spectroscopy over the last decade for a better understanding of solid surfaces, adsorption, surface reactivity, and heterogeneous catalysis has been discussed. The review is illustrative rather than exhaustive, but nevertheless it is clear that during this period XPS and UPS have matured into well-accepted experimental methods capable of providing chemical information at the molecular level down to 10% or less of a monolayer. The information in its most rudimentary state provides a qualitative model of the surface at a more sophisticated level quantitative estimates are possible of the concentration of surface species by making use of escape depth and photoionization cross-section data obtained either empirically or by calculation. 

The vertical IPs of CO deserve special attention because carbon monoxide is a reference compound for the application of photoelectron spectroscopy (PES) to the study of adsorption of gases on metallic surfaces. Hence, the IP of free CO is well-known and has been very accurately measured [62]. A number of very efficient theoretical methods specially devoted to the calculation of ionization energies can be found in the literature. Most of these are related to the so-called random phase approximation (RPA) [63]. The most common formulations result in the equation-of-motion coupled-cluster (EOM-CC) equations [59] and the one-particle Green s function equations [64,65] or similar formalisms [65,66]. These are powerful ways of dealing with IP calculations because the ionization energies are directly obtained as roots of the equations, and the repolarization or relaxation of the MOs upon ionization is implicitly taken into account [59]. In the present work we remain close to the Cl procedures so that a separate calculation is required for each state of the cation and of the ground state of the neutral to obtain the IP values. 

A recent paper by Lairdinvestigated the efficacy of HPAM flocculation of kaolinite, illite and quartz by carrying out visible absorption experiments. He concluded that HPAM more effectively flocculates kaolinite than quartz or illite. This was also the conclusion of previous work by Allen et al. who studied the adsorption of HPAM onto kaolinite, quartz and feldspar at various HPAM concentrations and solution pH by X-ray photoelectron spectroscopy (XPS). Much of the previous work on polyacrylamide adsorption onto aluminosilicates monitored the adsorbed amount by viscometry, carbon analysis and radiotracer techniques. These methods rely on following adsorption by subtraction from that detected in solution. 

This paper contributes to the literature by quantifying anionic polymer adsorption onto the clay minerals kaolinite, feldspar, mica and quartz by X-ray photoelectron spectroscopy (XPS). XPS measures the sorbed amount directly rather than by a subtraction technique. This enables an insight into how effective selective flocculation is for obtaining kaolinite from a mineral mixture. Atomic force microscopy (AFM) is also used to image polymer adsorption onto mineral surfaces and the effectiveness of this technique applied to mineral surfaces is discussed here. 

X ray photoelectron spectroscopy (XPS) is powerful in identifying species present at the surface/interface and atoms or functional groups involved in acid-base interactions [116]. Since XPS measures the kinetic energy of photoelectrons emitted from the core levels of surface atoms upon X ray irradiation of the uppermost atomic layers, it can be used to characterize surface acid sites, in combination with base probe molecules adsorption. 

In this work, we will show that the addition of TCM to the feedstream in the methane conversion process results in the enhancement of the conversion of methane and the selectivity to C2 hydrocarbons on praseodymium oxide primarily as a result of the formation of praseodymium oxychloride, in contrast with the production of carbon oxides on praseodymium oxide in the absence of TCM (8-10). The surface properties of these catalysts are characterized by application of adsorption experiments and X-ray photoelectron spectroscopy (XPS). 

Evidently, adsorption of chemical compounds at gold surfaces via specific Au—S interactions has heen very intensively studied for the last twenty years. In a recent review [90], Vericat et al. have described their own results of electrochemical, in situ STM, X-ray photoelectron spectroscopy (XPS), and SXD studies on adsorption of sulfur on Au(lll). It has been stated that S—Au bonds determine the structure and adsorption/desorption kinetics for both S — Au (111) and alkanethi-olate/Au(lll) systems in NaOH. 

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